Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • A61K6/893—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
  • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/92—Polyurethane having terminal ethylenic unsaturation

Definitions

• the invention relates to new (meth) acrylic acid derivatives containing urethane groups, their preparation and their use as monomeric components for dental materials.
• EP-A 0 017 936 describes acrylic acid esters and methacrylic acid esters of pentaerythritol.
• the monomers described there, in combination with inorganic fillers, give dental materials which have an undesirable polymerization shrinkage, which leads to a gap formation between tooth and filling material.
• US Pat. No. 4,554,336 describes urethane group-containing (meth) acrylic acid derivatives for adhesives in the dental field in which the urethane groups are substituted by a residue containing a (meth) acrylate group are.
• these compounds show insufficient properties, in particular a strength which is too low for practical use.
• New (meth) acrylic acid derivatives of the formula (I) containing urethane groups in the A is a straight-chain or branched, aliphatic radical with 2 to 20 carbon atoms, optionally containing 1 to 3 oxygen bridges, an aromatic radical with 6 to 24 carbon atoms, an araliphatic radical with 7 to 26 carbon atoms or a cycloaliphatic radical with 6 to 26 carbon atoms
• r represents the number of chains starting from A and denotes a number from 2 to 6
• R1 and R2 are the same and are hydrogen or different and are hydrogen and methyl
• n independently represents a number from 0 to 5 for each chain starting from A
• X is a divalent, straight-chain or branched aliphatic radical with 2 to 24 carbon atoms
• an aromatic radical with 6 to 26 carbon atoms is an araliphatic radical with 7 to 26 carbon atoms or a mono-cycloaliphatic radical with 6 to 26 carbon atoms, where the alipha
• Dental materials which are based on the (meth) acrylic acid derivatives containing urethane groups according to the invention, surprisingly show a significantly lower polymerization shrinkage and greater strength, and are therefore particularly suitable for use in practice.
• An aliphatic radical (A) can be a straight-chain or branched hydrocarbon radical having 2 to 20, preferably 3 to 12, carbon atoms.
• the following aliphatic radicals may be mentioned, for example:
• An aromatic radical (A) can be an aromatic hydrocarbon radical having 6 to 24, preferably 6 to 14, carbon atoms.
• the following aromatic radicals may be mentioned, for example:
• An araliphatic radical (A) can be a hydrocarbon radical having a straight-chain or branched aliphatic and an aromatic part with 7 to 26 carbon atoms, the aromatic part preferably containing 6 to 12 and the aliphatic part preferably 1 to 14 carbon atoms.
• the following araliphatic radicals may be mentioned, for example:
• a cycloaliphatic radical (A) can be a cyclic hydrocarbon radical having 6 to 26 carbon atoms, preferably 6 to 14 carbon atoms.
• the following cycloaliphatic radicals may be mentioned, for example:
• the radicals A can, preferably in the alphatic or cycloaliphatic part, contain 1 or 2, preferably 1, oxygen atoms, so that, for example, aliphatic or cycloaliphatic ethers are present.
• radicals A are particularly preferred: ethylene, propylene, 2,2-bismethylene-butan-1-yl, 2,2-bismethylene-propan-1-yl, 2,2-bis-methylene-propane-1,3 -diyl, 1,1 ⁇ -oxy-bis - [(2,2-methylene) propane-1,3-diyl], propane-1,2,3-triyl, 1,6-hexamethylene, 1,4-tetramethylene , 1,4-phenylene, xylylene, 1,4-cyclohexylene, 1,4-bismethylene-1,4-cyclo hexane, 2,2-bis (1,4-phenylene) propane, 3 (4), 8 (9) bis-methylene-tricyclo [5.2.1.0 2,6 ] decane and its isomers, 4 (5), 9-bismethylene-3,8-dimethyltricyclo [5.2.1.0 2,6 ] decane.
• radicals 2,2-bismethylene butan-1-yl, propane-1,2,3-triyl, 2,2-bismethylene propane-1,3-diyl and 3 (4), 8 (9) bismethylene are particularly preferred -Tricyclo [5.2.1.0.-2.6] decane.
• a divalent, straight-chain or branched aliphatic radical (X) can mean a hydrocarbon radical having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms. Examples include the following divalent aliphatic radicals: ethylene, propylene, 1,4-tetramethylene, 1,6-hexamethylene or 2,2,4-trimethyl-1,6-hexamethylene and isomers.
• a divalent aromatic radical (X) can mean an aromatic hydrocarbon radical having 6 to 26, preferably 6 to 18, carbon atoms.
• the following aromatic radicals may be mentioned, for example:
• a divalent araliphatic radical (X) can be a hydrocarbon radical having a straight-chain or branched aliphatic and an aromatic part with 7 to 20 carbon atoms, the aromatic part preferably containing 6 to 12 and the aliphatic preferably 1 to 8 carbon atoms.
• the following araliphatic radicals may be mentioned, for example:
• a divalent monocycloaliphatic radical (X) can mean a hydrocarbon radical having 6 to 26, preferably 6 to 14, carbon atoms. Examples include:
• Optionally substituted methylene groups can, for example, the groups be.
• a trivalent hydrocarbon radical (Z) can be a straight-chain or branched aliphatic hydrocarbon having 3 to 15 carbon atoms, preferably 3 to 10, carbon atoms.
• the radical Z can optionally contain 1 to 3 oxygen bridges, preferably 1 to 2 oxygen bridges. It is also possible for the Z radical to be substituted by 1 to 3, preferably 1 to 2 (meth) acrylate radicals. For example, the following residues are mentioned:
• Urethane group-containing (meth) acrylic acid derivatives of the formula (I) are preferred in which A is a straight-chain or branched, aliphatic radical with 3 to 12 carbon atoms, optionally containing 1 to 3 oxygen bridges, an aromatic radical with 6 to 14 carbon atoms, an araliphatic radical with 7 to 26 carbon atoms or a cycloaliphatic radical with 6 to 14 carbon atoms, r represents the number of chains starting from A and denotes a number from 2 to 6, R1 and R2 are the same and are hydrogen or different and are hydrogen and methyl, n for each chain starting from A independently of a number from 0 to 5, X is a divalent, straight-chain or branched aliphatic radical having 2 to 12 carbon atoms, or a monocycloaliphatic radical having 6 to 14 carbon atoms, or an aromatic radical having 6 to 18 carbon atoms, 1 to 3 of the aliphatic, monocycloaliphatic or aromatic radicals also being substituted via optional
• A for the 2,2-bismethylene-butan-1-yl residue, propane
• a process for the preparation of the (meth) acrylic acid derivatives of the formula (I) containing urethane groups according to the invention has also been in the A is a straight-chain or branched, aliphatic radical with 2 to 20 carbon atoms, optionally containing 1 to 3 oxygen bridges, an aromatic radical with 6 to 24 carbon atoms, an araliphatic radical with 7 to 26 carbon atoms or a cycloaliphatic radical with 6 to 26 carbon atoms, r represents the number of chains starting from A and denotes a number from 2 to 6, R1 and R2 are the same and are hydrogen or different and are hydrogen and methyl, n for each chain starting from A independently of a number from 0 to 5, X is a divalent, straight-chain or branched aliphatic radical with 2 to 24 carbon atoms, represents an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a monocycloaliphatic radical having 6 to 26 carbon atoms
• Diisocyanates of the formula III are known per se (EP 0 153 561) and can be prepared, for example, by reacting the diamines with phosgene.
• the isocyanaturethane is preferably purified by extraction with aliphatic solvents with boiling points below 120 ° C at normal pressure, e.g. with pentane, n-hexane, isopentane.
• Polyols of the formula IV are known per se (literature, for example DE-A 2 931 925) or are commercially available and can be prepared, for example, by oxyalkylating the known polyols of the formula A (OH) r , for example 2,2-bishydroxymethylbutane, 2,2- Bishydroxymethyl-propane-1,3-diol, 3 (4), 8 (9) -bishydroxymethyl-tricyclo [5.2.1.0 2,6 ] decane, etc. can be prepared. Due to the preparation, the polyols IV can also be present as a mixture of oxyalkylation products with a variable chain length.
• Inert solvents are generally used for the process according to the invention. Examples include acetone, chloroform, tetrahydrofuran, dioxane, methylene chloride, toluene and acetonitrile. Chloroform, toluene, acetonitrile and acetone are particularly preferred.
• the process according to the invention is carried out with the exclusion of water.
• Catalysts for the process according to the invention are generally metal salts of higher fatty acids.
• Preferred catalysts can be, for example, dibutyltin laurate, dibutyltin methoxide and tin (II) octoate.
• compounds with tertiary amino groups such as triethylamine, pyridine, 2-methylpyridine, N, N-dimethylpiperazine and N, N-dimethylbenzylamine, can also be used as catalysts. It is also possible to use titanium compounds such as tetrabutyl titanate.
• the catalyst will be used in an amount of 0.1 to 2.5% by weight, preferably 0.1 to 1.5% by weight, based on the total amount of the reactants.
• the process according to the invention can be carried out in the presence of a polymerization inhibitor.
• Polymerization inhibitors are known per se (Ullmanns Enzyklopadie der techn. Chemie, 4th edition, Verlag Chemie Weinheim, Volume 8, pages 19-45).
• 2,6-di-tert-butyl-4-methylphenol, hydroquinone, hydroquinone monomethyl ether may be mentioned.
• oxygen for example atmospheric oxygen
• the polymerization inhibitor which is introduced into the reaction mixture.
• the polymerization inhibitor is used in an amount of from 0.01 to 1.0% by weight, preferably from 0.01 to 0.2% by weight.
• the first stage of the process according to the invention is generally carried out in the temperature range from 0 to 120 ° C., preferably from 30 to 70 ° C.
• the second stage of the process according to the invention is generally carried out in the temperature range from 0 to 120 ° C., preferably from 30 to 70 ° C.
• the process according to the invention is generally carried out at normal pressure. However, it is also possible to carry out the process according to the invention at negative or positive pressure (for example in the pressure range from 0.1 to 10 bar).
• the method according to the invention can be carried out, for example, as follows:
• the (meth) acrylic acid ester of the formula (I) and, if appropriate, the polymerization inhibitor are dissolved in the inert solvent and added dropwise with stirring to the optionally dissolved diisocyanate (III).
• the catalyst is added to one of the two reactants.
• the reactants are reacted in a molar ratio of about 1: 1 to 1: 6 and carried out until the OH groups have completely converted or the isocyanate groups have reacted appropriately.
• the conversion of the isocyanate groups can be controlled in a known manner by IR spectroscopy and / or by titration.
• the isocyanaturethane obtained in the first stage is reacted with a polyol of the formula IV, optionally after extraction of any excess diisocyanate, so that the number of hydroxyl equivalents of the polyol corresponds approximately to the number of NCO equivalents still present.
• reaction is generally carried out until conversion is complete, so that neither free isocyanate nor polyol remain in the reaction.
• the reaction product is isolated by removing the solvent. Filtration or cleaning with the aid of adsorbents or activated carbon, bleaching earth, silica gel or aluminum oxide is possible.
• the process according to the invention generally produces a mixture of (meth) acrylic acid derivatives containing urethane groups, which can be separated on adsorbents.
• the new urethane (meth) acrylates in the dental field, however, it is not necessary to separate the reaction mixtures obtained.
• the mixtures themselves can advantageously be used as a component of dental materials, for example tooth filling materials.
• Diisocyanates suitable for this purpose are, in particular, those which, in addition to a sterically unhindered, aliphatically bound, and a sterically hindered, cycloaliphatically bound isocyanate groups, include, for example:
• the urethane (meth) acrylic acid derivatives according to the invention can be used in particular as monomers for dental materials.
• Dental materials include, for example, filling materials for teeth, coating compositions for teeth and components for the production of dentures, preferably plastic teeth. Depending on the area of application, dental materials can contain further additives.
• the (meth) acrylic acid derivatives according to the invention can be used as monomers for polymerizable tooth filling compounds or coating agents in the dental field are mixed with monomers known per se, for example in order to adapt the viscosity to the intended use. Viscosities in the range from 60 to 10,000 mPas are preferred. This can be achieved by optionally adding a low viscosity comonomer as reactive diluent or solvent to the monomers according to the invention.
• the compounds according to the invention are present in the monomer mixture in a proportion of approximately 30 to approximately 90% by weight, preferably 40 to 80% by weight. It is also preferred to use mixtures of various (meth) acrylic acid derivatives according to the invention.
• Glycerol di (meth) acrylate triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol dimethacrylate, 2,2-bis- [p- (2 ⁇ -hydroxy-3 ⁇ -methacryloyloxy propoxy) phenyl] propane, 2,2-bis- [p- (2 ⁇ -methacryloyloxyethoxy) phenyl] propane, trimethylol propane tri- (meth) acrylate, bis- (meth) acryloyloxyethoxymethyltricyclo- [5,2,1,0 2,6 ] -decane DE-A 29 31 925 and DE-A 29 31 926).
• Comonomers which have a boiling point above 100 ° C. at 13 mbar are particularly preferred.
• the polyfunctional (meth) acrylic acid esters according to the invention can optionally cure in a mixture with the comonomers mentioned using known methods to form crosslinked polymers (Am. Chem. Soc., Symp. Ser. 212 , 359-371 (1983)).
• a system consisting of a peroxidic compound and a reducing agent, for example based on tertiary aromatic amines, is suitable for the so-called redox polymerization.
• peroxides are: dibenzoyl peroxide, dilauroyl peroxide and di-4-chlorobenzoyl peroxide.
• tertiary aromatic amines are N, N-dimethyl-p-toluidine, bis- (2-hydroxyethyl) -p-toluidine, bis- (2-hydroxyethyl) -3,5-dimethylaniline and N-methyl-N- (2 -methylcarbamoyloxypropyl) -3,5-dimethylaniline called.
• concentrations of the peroxide or of the amine are advantageously chosen such that they are 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the monomer mixture.
• the peroxide- or amine-containing monomer mixtures are stored separately until use.
• the monomers according to the invention can also be brought to polymerization by irradiation with UV light or visible light (for example in the wavelength range from 230 to 650 nm).
• Suitable initiators for the photo-initiated polymerization are, for example, benzil, benzil dimethyl ketal, benzoin monoalkyl ether, benzophenone, p-methoxybenzophenone, fluorenone, thioxanthone, phenanthrenequinone and 2,3-bornanedione (camphorquinone), optionally in the presence of synergistic agents Activators such as N, N-dimethylaminoethyl methacrylate, triethanolamine, 4-N, N-dimethylaminobenzenesulfonic acid diallylamide.
• the implementation of the photopolymerization is described for example in DE-A 3 135 115.
• the light stabilizers and stabilizers known per se for this purpose can be added to the (meth) acrylic acid derivatives according to the invention.
• Light stabilizers are described, for example, in (Gommeter, Müller, Taschenbuch der Kunststoff-Additive, 2nd Edition, Carl Hanser Verlag). Examples include the following light stabilizers: Cyasorb UV9®, Tinuvin P®, Tinuvin 770®, Tinuvin 622®, Tinuvin 765®.
• Stabilizers are described, for example, in (Ullmanns Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 8). For example, the following stabilizers are mentioned: 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-octadecyl-4-methylphenol, 1,1 ⁇ -Methylene-bis (naphthol-2) and others
• the light stabilizers and the stabilizers can each be used in an amount of 0.01 to 0.5 parts by weight, based on 100 parts by weight of the monomer mixture.
• the monomer mixtures can be used as coating agents (tooth varnishes) without the addition of fillers.
• fillers When used as tooth filling compounds, fillers are generally added to the monomer mixtures obtained. In order to be able to achieve a high degree of filling, monomer mixtures which have a viscosity in the range from 60 to 10,000 mPas are particularly advantageous.
• Inorganic fillers are preferably added to the (meth) acrylic acid derivatives according to the invention.
• rock crystal, crystal ballite, quartz glass, highly disperse silica, aluminum oxide and glass ceramics, for example glass ceramics containing lanthanum and zircon (DE-A 2 347 591) may be mentioned.
• the inorganic fillers are preferably pretreated with an adhesion promoter. Half-mediation can be achieved, for example, by treatment with organosilicon compounds (Progress in Organic Coatings 11 , 297-308 (1983)).
• 3-Methacryloyloxypropyltrimethoxysilane is preferably used.
• the fillers for the dental filling compositions according to the invention generally have an average particle diameter of 0.01 to 100 ⁇ m, preferably 0.03 to 50 ⁇ m, particularly preferably 0.03 to 5 ⁇ m. It can also be advantageous to use several fillers next to one another which have a different particle diameter and / or a different silane content.
• the proportion of filler in the tooth filling compound is generally 5 to 85% by weight, preferably 50 to 80% by weight.
• the components are mixed using commercially available kneading machines.
• the proportion of the urethane (meth) acrylates according to the invention in the dental filling materials is generally 5 to 70% by weight, based on the filling material.
• the tooth lacquers and tooth filling compositions according to the invention surprisingly have a particularly low polymerization shrinkage and good mechanical strengths, in particular high hardness and excellent wear resistance.
• the urethane (meth) acrylic acid derivatives according to the invention can also be used as components in the manufacture of dentures.
• the monomers according to the invention are combined with the commonly used constituents known per se.
• the monomers are preferably used in a mixture with alkyl methacrylates, such as methyl methacrylate.
• alkyl methacrylates such as methyl methacrylate.
• Known bead polymers can also be added.
• Known inorganic and organic color pigments and opacifiers can be added to adjust the tooth shade. Stabilizers and light stabilizers can also be used.
• the plastic teeth are produced by radical polymerisation of the dental materials with shaping.
• Processing is possible both by injection methods and by embossing methods and is generally carried out according to the usual manufacturing methods for teeth based on poly (methyl methacrylate), e.g. by thermal polymerization using known polymerization initiators, for example based on peroxides and azo compounds such as dibenzoyl peroxide, dilauroyl peroxide, cyclohexyl percarbonate, azobisisobutyronitrile. Mixtures of polymerization initiators with different decomposition temperatures are also very suitable.
• the dental materials produced from the (meth) acrylic acid esters according to the invention are notable for high resistance to mechanical stress and high abrasion resistance.
• reaction mixture is filtered through activated carbon and freed from solvent by evaporation. A highly viscous liquid is obtained.
• Example 1 was repeated, except that 22.2 g of isophorone diisocyanate were used instead of hexamethylene diisocyanate was set and a reaction time of 28 h was observed in the second reaction stage. A white solid is obtained.
• the mixture is filtered through silica gel and the solvent is stripped off on a rotary evaporator.
• the product is a highly viscous, colorless liquid.
• the product is a colorless, highly viscous liquid.
• TEGDMA triethylene glycol dimethacrylate
• the percentages relate to the sum of urethane (meth) acrylate and triethylene glycol dimethacrylate.
• the activated mixtures were cured with a commercial dental lamp (Translux, Kulzer) to solid test specimens.
• the flexural strength of these test specimens was determined in accordance with DIN 13922 and a hardness test was carried out using the Wallace method.
• the Wallace method is used to determine the indentation hardness on plastics.
• a Vickers diamond is applied to the surface under a preload of 1 p and then subjected to a main load of typically 100 p for 60 seconds.
• the penetration depth of the diamond under main load is measured as a measure of the penetration resistance.
• the elastic and permanent deformation of the plastic is recorded with the Wallace method.
• This method is more suitable for the characterization of materials for applications in the dental field than hardness tests, which only record the permanent deformation.
• the activated mixture is injected into a tooth mold and cured at 130 ° C in 6 minutes.
• the plastic teeth obtained show a particularly high abrasion resistance.

Landscapes

• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Epidemiology (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Dental Preparations (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=25845929

Family Applications (2)

Family Applications Before (1)

Country Status (5)

Families Citing this family (49)

Family Cites Families (7)

• 1987
  • 1987-02-03 DE DE19873703130 patent/DE3703130A1/de not_active Withdrawn
  • 1987-07-10 US US07/072,467 patent/US4879402A/en not_active Expired - Lifetime
  • 1987-07-14 ES ES198787110819T patent/ES2038627T3/es not_active Expired - Lifetime
  • 1987-07-14 EP EP87110819A patent/EP0264551B1/fr not_active Expired - Lifetime
  • 1987-07-14 DE DE8787110819T patent/DE3767270D1/de not_active Expired - Lifetime
  • 1987-07-21 EP EP87110510A patent/EP0254263A2/fr not_active Withdrawn
  • 1987-07-22 JP JP62181283A patent/JP2555364B2/ja not_active Expired - Lifetime
• 1989
  • 1989-07-13 US US07/379,128 patent/US4952241A/en not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events